Semi-quantitative design of synergetic surficial/interfacial sites for the semi-continuous oxidation of glycerol
Qualitatively identifying the dominant catalytic site for each step of a semi-continuous reaction and semi-quantitatively correlating such different sites to the catalytic performance is of great significance toward the integration of multiple well-optimized sites on a heterogeneous catalyst. Herein...
| Main Authors: | , , , , , |
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| Format: | Article |
| Language: | English |
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KeAi Communications Co. Ltd.
2022-05-01
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| Series: | Fundamental Research |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2667325821001606 |
| _version_ | 1797976311679942656 |
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| author | Mingyu Gao Pengfei Yang Xinyi Zhang Yani Zhang Dianqing Li Junting Feng |
| author_facet | Mingyu Gao Pengfei Yang Xinyi Zhang Yani Zhang Dianqing Li Junting Feng |
| author_sort | Mingyu Gao |
| collection | DOAJ |
| description | Qualitatively identifying the dominant catalytic site for each step of a semi-continuous reaction and semi-quantitatively correlating such different sites to the catalytic performance is of great significance toward the integration of multiple well-optimized sites on a heterogeneous catalyst. Herein, a series of structurally defined TiOx-based catalysts were synthesized to provide a feasible approach to investigate the aforementioned issues using the semi-continuous oxidation of glycerol as a model reaction. Detailed investigations have verified the simultaneous presence of two kinds of Pt active sites: 1) Negatively charged Pt bound to the oxygen vacancies of modified TiOx in the form of Ptδ−-Ov-Ti3+ sites and 2) metallic Pt (Pt0 site) located away from the interface. Meanwhile, the proportion of surficial and interfacial sites varies over this series of catalysts. Combined in situ FTIR experiments revealed that the reaction network was well-tuned via a site cooperation mechanism: The surficial Pt0 sites dissociatively adsorb the OH group of glycerol with a monodentate bonding geometry and the Ptδ−-Ov-Ti3+ sites dissociate the C=O bond of the aldehyde group in a bidentate form. Furthermore, CO-FTIR spectroscopy confirmed a correlation between the reaction rate/product selectivity and the fraction of surficial/interfacial sites. A rational proportion of surficial and interfacial sites is key to enabling a high yield of glyceric acid. The most active catalyst with 32% surface sites and 68% interfacial sites exhibited 90.0% glycerol conversion and 68.5% GLYA selectivity. These findings provide a deeper understanding of the structure-activity relationships using qualitative identification and semi-quantitative analysis. |
| first_indexed | 2024-04-11T04:49:00Z |
| format | Article |
| id | doaj.art-9b930936aaae41d2b2088d7127bc2e0b |
| institution | Directory Open Access Journal |
| issn | 2667-3258 |
| language | English |
| last_indexed | 2024-04-11T04:49:00Z |
| publishDate | 2022-05-01 |
| publisher | KeAi Communications Co. Ltd. |
| record_format | Article |
| series | Fundamental Research |
| spelling | doaj.art-9b930936aaae41d2b2088d7127bc2e0b2022-12-27T04:42:21ZengKeAi Communications Co. Ltd.Fundamental Research2667-32582022-05-0123412421Semi-quantitative design of synergetic surficial/interfacial sites for the semi-continuous oxidation of glycerolMingyu Gao0Pengfei Yang1Xinyi Zhang2Yani Zhang3Dianqing Li4Junting Feng5State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, 100029, ChinaState Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, 100029, ChinaState Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, 100029, ChinaState Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, 100029, ChinaState Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, 100029, China; Beijing Engineering Center for Hierarchical Catalysts, Beijing University of Chemical Technology, Beijing, 100029, ChinaState Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, 100029, China; Beijing Engineering Center for Hierarchical Catalysts, Beijing University of Chemical Technology, Beijing, 100029, China; Corresponding author.Qualitatively identifying the dominant catalytic site for each step of a semi-continuous reaction and semi-quantitatively correlating such different sites to the catalytic performance is of great significance toward the integration of multiple well-optimized sites on a heterogeneous catalyst. Herein, a series of structurally defined TiOx-based catalysts were synthesized to provide a feasible approach to investigate the aforementioned issues using the semi-continuous oxidation of glycerol as a model reaction. Detailed investigations have verified the simultaneous presence of two kinds of Pt active sites: 1) Negatively charged Pt bound to the oxygen vacancies of modified TiOx in the form of Ptδ−-Ov-Ti3+ sites and 2) metallic Pt (Pt0 site) located away from the interface. Meanwhile, the proportion of surficial and interfacial sites varies over this series of catalysts. Combined in situ FTIR experiments revealed that the reaction network was well-tuned via a site cooperation mechanism: The surficial Pt0 sites dissociatively adsorb the OH group of glycerol with a monodentate bonding geometry and the Ptδ−-Ov-Ti3+ sites dissociate the C=O bond of the aldehyde group in a bidentate form. Furthermore, CO-FTIR spectroscopy confirmed a correlation between the reaction rate/product selectivity and the fraction of surficial/interfacial sites. A rational proportion of surficial and interfacial sites is key to enabling a high yield of glyceric acid. The most active catalyst with 32% surface sites and 68% interfacial sites exhibited 90.0% glycerol conversion and 68.5% GLYA selectivity. These findings provide a deeper understanding of the structure-activity relationships using qualitative identification and semi-quantitative analysis.http://www.sciencedirect.com/science/article/pii/S2667325821001606Synergistic effectSurficial sitesInterfacial sitesSemi-continuous reactionsSemi-quantitative analysis |
| spellingShingle | Mingyu Gao Pengfei Yang Xinyi Zhang Yani Zhang Dianqing Li Junting Feng Semi-quantitative design of synergetic surficial/interfacial sites for the semi-continuous oxidation of glycerol Fundamental Research Synergistic effect Surficial sites Interfacial sites Semi-continuous reactions Semi-quantitative analysis |
| title | Semi-quantitative design of synergetic surficial/interfacial sites for the semi-continuous oxidation of glycerol |
| title_full | Semi-quantitative design of synergetic surficial/interfacial sites for the semi-continuous oxidation of glycerol |
| title_fullStr | Semi-quantitative design of synergetic surficial/interfacial sites for the semi-continuous oxidation of glycerol |
| title_full_unstemmed | Semi-quantitative design of synergetic surficial/interfacial sites for the semi-continuous oxidation of glycerol |
| title_short | Semi-quantitative design of synergetic surficial/interfacial sites for the semi-continuous oxidation of glycerol |
| title_sort | semi quantitative design of synergetic surficial interfacial sites for the semi continuous oxidation of glycerol |
| topic | Synergistic effect Surficial sites Interfacial sites Semi-continuous reactions Semi-quantitative analysis |
| url | http://www.sciencedirect.com/science/article/pii/S2667325821001606 |
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